CN104974754A - Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof - Google Patents
Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof Download PDFInfo
- Publication number
- CN104974754A CN104974754A CN201510376062.7A CN201510376062A CN104974754A CN 104974754 A CN104974754 A CN 104974754A CN 201510376062 A CN201510376062 A CN 201510376062A CN 104974754 A CN104974754 A CN 104974754A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- preparation
- fluorescent powder
- blue
- green
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a phosphate fluorescent powder with adjustable color from blue to green. The chemical formula is (Ca<1-x-y>Sr<x>Ba<y>)<8.955>MgNa(PO4)7:0.005Eu2+, wherein when 0<x<=1, y=0, and when x=0, 0<y<=1. The invention also provides a preparation method of the phosphate fluorescent powder. The preparation method comprises following steps: a calcium salt, a strontium salt, a barium salt, a sodium salt, basic magnesium carbonate, and europium oxide or europium nitrate are uniformly mixed with a phosphate, an obtained mixture is grinded, and is delivered into a corundum crucible, and the corundum crucible is delivered into a high temperature furnace; high temperature calcination is carried out in a reducing atmosphere, and an obtained product is subjected natural cooling, and is grinded into powder so as to obtain the phosphate fluorescent powder with adjustable color from blue to green. According to the preparation method, ion sites of Ca2+ are replaced by that of Ba2+ or Sr2+, crystal field environment is changed, luminescence spectrum of the fluorescent powder can be adjusted from blue to green, and color adjusting is realized.
Description
Technical field
The invention belongs to materialogy field, particularly relate to a kind of rare earth luminescent material, a kind of blue to adjustable phosphate phosphor of green color and preparation method thereof specifically.
Background technology
White light emitting diode (white light-emitting diodes, WLEDs), the remarkable advantage such as energy consumption low, pollution-free, efficiency high, volume little long with its life-span, have broad application prospects in illumination and display field, be called as lighting source of new generation.
The raising of ultraviolet/near ultraviolet chip research and development technology, makes the research and development of the three primary colors fluorescent powder being mated use become the major subjects in fluorescent material field.Phosphoric acid salt is because its preparation temperature is low, luminous efficiency is high, physicochemical property are stable, effectively can absorb UV photon energy, becomes the matrix of widespread use in fluorescent material research and development of today.
Ca
9mgNa (PO
4)
7: Eu
2+fluorescent material Eu
2+the luminescence of ion belongs to 4f
65d
1→ 4f
1transition luminescence, 5d
1energy state energy comparison is low, and be in the outermost layer of ion, electronics is exposed.Therefore 5d
1the engery level cracking degree of track affects very large by crystal field.And the crystal field environment of different substrates can affect Eu
2+the glow color of ion and intensity.We can be undertaken replacing the structure changing fluorescent material matrix by other elements, crystal field environment is changed, improves the luminescent properties of fluorescent material.Recent years, the exploration that adulterated alkaline-earth metal element carries out replacing in matrix causes to be paid close attention to widely.Ca, Sr and Ba belong to II A race, are alkaline-earth metal.But, also do not replace Ca about employing Sr, Ba at present
9mgNa (PO
4)
7: Eu
2+ca in fluorescent material
2+ion, changes its crystal field environment, regulates the emission wavelength of fluorescent material, to reach the report of the adjustable object of spectrum.
Summary of the invention
For the problems referred to above of the prior art, the invention provides a kind of blueness to adjustable phosphate phosphor of green color and preparation method thereof, described this fluorescent material preparation method achieves by replacing Ca
9mgNa (PO
4)
7substrate material intermediate ion carries out the technology regulating and controlling fluorescence, solves in prior art by means of only doping with rare-earth ions regulation and control luminescent properties problem.
The present invention is a kind of blue to the adjustable phosphate phosphor of green color, and its combination matching general formula is (Ca
1-x-ysr
xba
y)
8.955mgNa (PO
4)
7: 0.005Eu
2+, wherein when 0<x≤1, y=0; As x=0,0<y≤1.
Present invention also offers the preparation method of above-mentioned a kind of blueness to the adjustable phosphate phosphor of green color, Ca is taken according to mol ratio, Sr, Ba, Mg, Na, the compound that Eu is corresponding and phosphoric acid salt, by Ca, Sr, Ba, Mg, Na, grinding 10-30min is carried out after the compound that Eu is corresponding mixes with phosphoric acid salt, alcohol or acetone is added after grinding, mixture is obtained after again grinding 40-60min, mixture is loaded in corundum crucible, be placed in High Temperature Furnaces Heating Apparatus, 18-36 hour is calcined under temperature is the CO atmosphere of 1050-1300 DEG C or nitrogen and hydrogen mixture atmosphere, naturally cooling, namely Color tunable phosphate phosphor material is obtained, Ca
2+, Ba
2+, Sr
2+, Mg
2+, Na
+compound be selected from any one or more than one combination in its carbonate, nitrate, oxide compound, containing PO
4 2-compound be selected from any one or more than one combination in triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, containing Eu
2+compound be selected from europium sesquioxide or europium nitrate any one.
Color tunable phosphate phosphor provided by the invention, passes through Ba
2+or Sr
2+replace Ca
2+ion site, changes its crystal field environment, prepares luminescent spectrum from blueness to green color adjustable fluorescent powder, and its tristimulus coordinates changes to (0.2378,0.3635) from (0.1663,0.0263).
Accompanying drawing explanation
Fig. 1 is (Ca of the present invention
1-x-ysr
xba
y)
8.955mgNa (PO
4)
7: 0.005Eu
2+tristimulus coordinates figure.
Embodiment
embodiment 1:
Preparation Ca
8.955mgNa (PO
4)
7: 0.005Eu
2+.
Take calcium carbonate 0.482g, magnesium basic carbonate 0.0522g, sodium carbonate 0.0285g, europium sesquioxide 0.0043g, primary ammonium phosphate 0.433g, be placed in mortar ground and mixed 30min, then mixture is obtained after adding alcohol grinding 60min, mixture is put into corundum crucible and is placed in High Temperature Furnaces Heating Apparatus, under CO reducing atmosphere, 1050 DEG C of calcinings are after 24 hours, naturally cooling grind into powder.
embodiment 2:
Preparation (Ca
0.5sr
0.5)
8.955mgNa (PO
4)
7: 0.005Eu
2+.
Take calcium carbonate 0.2151g, Strontium carbonate powder 0.3204g, magnesium basic carbonate 0.0469g, sodium carbonate 0.0256g, europium sesquioxide 0.0038g, primary ammonium phosphate 0.3883g, be placed in mortar ground and mixed 30min, obtain mixture after then adding acetone grinding 10min, mixture is put into corundum crucible and is placed in High Temperature Furnaces Heating Apparatus, under CO reducing atmosphere, 1050 DEG C of calcinings are after 24 hours, naturally cooling grind into powder.
embodiment 3:
Preparation Sr
8.955mgNa (PO
4)
7: 0.005Eu
2+.
Take strontium nitrate 0.6443g, magnesium nitrate 0.0504g, SODIUMNITRATE 0.0289g, europium sesquioxide 0.0027g, primary ammonium phosphate 0.2737g, be placed in mortar ground and mixed 30min, then mixture is obtained after adding acetone grinding 10min, mixture is put into corundum crucible and is placed in High Temperature Furnaces Heating Apparatus, under hydrogen nitrogen mixed gas reducing atmosphere, 1300 DEG C of calcinings are after 3 hours, naturally cooling grind into powder.
embodiment 4:
Preparation (Ca
0.5ba
0.5)
8.955mgNa (PO
4)
7: 0.005Eu
2+.
Take nitrocalcite 0.2374, nitrate of baryta 0.3818g, magnesium nitrate 0.0482g, SODIUMNITRATE 0.0276g, europium nitrate 0.049g, Secondary ammonium phosphate 0.3001g, be placed in mortar ground and mixed 30min, obtain mixture after then adding alcohol grinding 60min, mixture is put into corundum crucible and is placed in High Temperature Furnaces Heating Apparatus, under hydrogen nitrogen mixed gas reducing atmosphere, 1300 DEG C of calcinings are after 36 hours, naturally cooling grind into powder.
embodiment 5:
Preparation Ba
8.955mgNa (PO
4)
7: 0.005Eu
2+.
Take nitrate of baryta 0.6823g, magnesium basic carbonate 0.0283g, sodium carbonate 0.0155g, europium nitrate 0.0044g, Secondary ammonium phosphate 0.2695g, be placed in mortar ground and mixed 30min, then mixture is obtained after adding alcohol grinding 60min, mixture is put into corundum crucible and is placed in High Temperature Furnaces Heating Apparatus, under CO reducing atmosphere, 1300 DEG C of calcinings are after 24 hours, naturally cooling grind into powder.
Claims (2)
1. blueness is to the adjustable phosphate phosphor of green color, it is characterized in that: its combination matching general formula is (Ca
1-x-ysr
xba
y)
8.955mgNa (PO
4)
7: 0.005Eu
2+, wherein when 0<x≤1, y=0; As x=0,0<y≤1.
2. a kind of blueness according to claim 1 is to the preparation method of the adjustable phosphate phosphor of green color, it is characterized in that: take compound corresponding to Ca, Sr, Ba, Mg, Na, Eu and phosphoric acid salt according to mol ratio, mix after carrying out grinding 50-90min and load corundum crucible, in the High Temperature Furnaces Heating Apparatus of the CO of 1050-1300 DEG C or nitrogen and hydrogen mixture atmosphere, calcine 18-36 hour, namely obtain Color tunable phosphate phosphor material; Ca
2+, Ba
2+, Sr
2+, Mg
2+, Na
+compound be selected from any one or more than one combination in its carbonate, nitrate, oxide compound; Containing PO
4 2-compound be selected from any one or more than one combination in triammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate; Containing Eu
2+compound be selected from europium sesquioxide or europium nitrate any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510376062.7A CN104974754A (en) | 2015-07-01 | 2015-07-01 | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510376062.7A CN104974754A (en) | 2015-07-01 | 2015-07-01 | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104974754A true CN104974754A (en) | 2015-10-14 |
Family
ID=54271730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510376062.7A Pending CN104974754A (en) | 2015-07-01 | 2015-07-01 | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104974754A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300466A (en) * | 2018-01-16 | 2018-07-20 | 北京科技大学 | A kind of red fluorescence powder and preparation method thereof |
| CN110129050A (en) * | 2019-06-12 | 2019-08-16 | 上海应用技术大学 | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051176A (en) * | 2009-10-27 | 2011-05-11 | 财团法人工业技术研究院 | Fluorescent material, manufacture method thereof and light-emitting device comprising fluorescent material |
| CN104498031A (en) * | 2014-11-26 | 2015-04-08 | 中国计量学院 | Phosphate yellow phosphor for white LED, and preparation method thereof |
-
2015
- 2015-07-01 CN CN201510376062.7A patent/CN104974754A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051176A (en) * | 2009-10-27 | 2011-05-11 | 财团法人工业技术研究院 | Fluorescent material, manufacture method thereof and light-emitting device comprising fluorescent material |
| CN104498031A (en) * | 2014-11-26 | 2015-04-08 | 中国计量学院 | Phosphate yellow phosphor for white LED, and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| CHIEN-HAO HUANG等: "(Ca,Mg,Sr)9Y(PO4)7:Eu2+,Mn2+: Phosphors for white-light near-UV LEDs through crystal field tuning and energy transfer", 《J. MATER. CHEM.》 * |
| JIA ZHANG等: "Luminescence of emission-tunable Ca10Li(PO4)7:Eu2+, Sr2+, Mn2+ phosphors with various Eu2+ centers for LED applications", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| JIA ZHANG等: "Warm white-lightgenerationinCa9MgNa(PO4)7:Sr2+, Mn2+, Ln (Ln＝Eu2+, Yb3+, Er3+, Ho3+, and Tm3+) undernear-ultraviolet and near-infraredexcitation", 《CERAMICS INTERNATIONAL》 * |
| MARK E. HANNAH等: "A Study of Blue Emitting Phosphors, ABPO4:Eu2+ (A=Li, Na, K; B=Ca, Sr, Ba) for UV LEDs", 《ECS TRANSACTIONS》 * |
| YUCHUN WANG等: "Investigations on the luminescence of emission-tunable Ca10K(PO4)7:Eu2+, Sr2+, Mg2+ phosphors for white LEDs", 《RSC ADV.》 * |
| ZHIGUO XIA等: "Identification of the crystallographic sites of Eu2+ in Ca9NaMg(PO4)7: structure and luminescence properties study", 《DALTON TRANS.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108300466A (en) * | 2018-01-16 | 2018-07-20 | 北京科技大学 | A kind of red fluorescence powder and preparation method thereof |
| CN110129050A (en) * | 2019-06-12 | 2019-08-16 | 上海应用技术大学 | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method |
| WO2020248973A1 (en) * | 2019-06-12 | 2020-12-17 | 上海应用技术大学 | Single-doped single-phase full-spectrum fluorescent powder and preparation method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yongqing et al. | Properties of red-emitting phosphors Sr2MgSi2O7: Eu3+ prepared by gel-combustion method assisted by microwave | |
| CN105038787A (en) | Ce, Tb and Mn-coactivated single-matrix phosphate white phosphor powder and preparation method thereof | |
| Cao et al. | Tunable multicolor luminescent properties of Ca8ZnLa (PO4) 7: Ce3+, Mn2+ phosphor via efficient energy transfer | |
| CN105038779B (en) | A kind of Eu3+/Eu2+The aluminate multicolor fluorescence material and preparation method of doping | |
| Yang et al. | Luminescence properties and energy transfer investigations of Sr3Lu (PO4) 3: Ce3+, Tb3+ phosphors | |
| CN104877675A (en) | Mixed-valence-state europium (Eu) ion doped single-matrix color-adjustable fluorescent powder and preparation method thereof | |
| Lai et al. | Thermally stable luminescence properties and energy transfer of green-emitting LiBaPO4: Tb3+, Ce3+ Phosphor | |
| Zhong et al. | The self-reduction synthesis and luminescent properties of color-tunable BaSnxSi3O7+ 2x: Eu2+-Eu3+ phosphors with high quantum efficiency for white light-emitting diodes | |
| Ren et al. | High quantum efficiency and luminescence properties of far-red Sr3NaTaO6: Mn4+, Ba2+ phosphor for application in plant growth lighting LEDs | |
| Dai et al. | Controllable luminescence and efficient energy transfer investigation of a novel white light emission phosphor Ca19Na2Mg (PO4) 14: Dy3+, Tm3+ with high thermal stability | |
| CN102585818B (en) | Rare earth niobium tantalate fluorescent powder with adjustable luminous chroma, preparation method and application thereof | |
| Zhao et al. | Synthesis and photoluminescent properties of orange-emitting Sm3+-activated KPb4 (PO4) 3 phosphor for LEDs | |
| CN102127441A (en) | Eu<2+> activated strontium pyrophosphate photoluminescence material and preparation method thereof | |
| CN100386405C (en) | Red long afterglow luminescent material and its prepn | |
| CN104974754A (en) | Phosphate fluorescent powder with adjustable color from blue to green, and preparation method thereof | |
| US9045690B2 (en) | Silicate luminescent material and production method thereof | |
| CN104531144A (en) | CaMg<2>Al<16>O<27>:Mn <4+> red fluorescent powder and preparation technology thereof | |
| Lv et al. | Sr3GdLi (PO4) 3F: Eu2+, Mn2+: A tunable blue-white color emitting phosphor via energy transfer for near-UV white LEDs | |
| CN107163943B (en) | Spectrum-adjustable fluorescent powder suitable for near ultraviolet excitation and preparation method thereof | |
| CN105400512A (en) | Red tungstate fluorescent powder as well as preparation method and application thereof | |
| CN105542769A (en) | Green phosphor for white LED and preparation method thereof | |
| CN104830335A (en) | Europium-doped borate fluorescent powder and preparing method thereof | |
| CN110373188B (en) | Ultraviolet excited Eu single-doped single-phase white light emitting fluorescent powder and preparation method thereof | |
| CN104974756B (en) | Cerium and terbium mono-doped/codoped yttrium sodium phosphate fluorescent powder, and preparation method thereof | |
| Zhai et al. | Microwave synthesis and luminescence properties of PO43− and alkali metal ions-doped CaMoO4: Dy3+ phosphors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151014 |